Oil- and water-repellent polymeric compositions



United States Patent Ofiice 3,546,187 Patented Dec. 8, 1970 3,546,187OIL- AND WATER-REPELLENT POLYMERIC COMPOSITIONS Thomas K. Tandy, Jr..,Newark, Del., assignor to E. I. du Pont de Nemours and Company,Wilmington, Del., a corporation of Delaware No Drawing. Filed Mar. 10,1969, Ser. No. 805,814 Int. Cl. C08f 15/26 U.S. Cl. 26080.76 22 ClaimsABSTRACT OF THE DISCLOSURE An oiland water-repellent polymer consistingessentially of:

(a) from 75% to 98% by weight of units derived from monomers ofstructure R CH CH O CCH=CH wherein R is a perfluoroalkyl group of fromfour to fourteen carbons;

(b) from 25% to 2% by weight of units derived from monomers selectedfrom the class consisting of (1) ROCH=CH wherein R is selected from X(CF),,CH X being F or H and n one or two, and (CF CH, and

(2) R'OCF=CF wherein R is selected from R, as defined above, and F(CF mbeing from one to three; and

(c) from to by weight of units derived from monomers selected from theclass consisting of (1) CH CR CONHR OH,

(2) CH CR CO R OH, and

(3) CH CR CO R wherein R is H or CH R is an alkylene group of from oneto about four carbons, R is an alkylene group of from two to about fourcarbons and R is epoxyalkyl of at least three carbons; or

(4) mixtures of the above;

and wherein the total percent by weight of units present in thecopolymer is 100%.

Preferably the polymers have an inherent viscosity as 0.5% solutions intrichlorotrifluoroethane at 30 C. not in excess of 0.8, and mostpreferably in the range of 0.1 to 0.35.

BACKGROUND OF THE INVENTION This invention is concerned with newfluorinated oil and water repellents for textiles. More specifically,the invention is directed to such polymers containing and trifluoroethylvinyl ether.

A wide variety of fluorine-containing polymeric materials are known tobe useful for treating textiles to render the textiles oil and waterrepellent. Such fluorinated polymers usually have their fluorine in theform of pendent perfiuoroalkyl groups as fluorine attached to thepolymer backbone does not, in general, greatly contribute to oil andwater repellency. While oil and water repellency of a good degree can beobtained and can be made durable to laundering and dry-cleaning, theknown oiland waterrepellent fluorinated polymers are deficient inseveral respects. Some of these deficiencies have limited commercialacceptance of textiles treated with fluorinated oil and waterrepellents.

The deficiencies are discussed in the immediate paragraphs below.

First, most if not all of these fluorinated polymertreated textiles losetheir oil and water repellency after laundering when the textile isdried in air at ambient temperatures. The repellency can in large partbe restored by heating as, for example, during pressing or during dryingin a heated drier. This lack of repellency after the socalled homewash-air dry laundering has greatly affected usefulness of thefluorinated oil and water repellents in the permanent press garmentmarket, for example, where the entire purpose of the permanent presstreatment is to obviate the necessity for pressing or heated drying. Asecond facet of this problem is, of course, that the laundered fabricslack any protection provided by oil repellency in particular betweenlaundering and the pressing or heated drying which otherwise restoresrepellency. The polymers of this invention continue to impart oil andwater repellency to textiles after laundering and air drymg.

Second, all of the presently known fluorinated oiland water-repellentpolymer systems require a rather high temperature cure after applicationto develop repellency. The permanent press resins used in textiles alsorequire rather high temperature cures but such cure cannot be applieduntil after the textile is converted into the final form of the garmentand the desired creases applied. Thus, textiles treated with permanentpress resins and presently available oil and Water repellents cannot becured until the garment is complete and therefore do not have any oilandwater-repelling properties until the garment is complete. Consequently,a large amount of such textile is soiled by oils and greases duringgarment manufacture without any benefit being gained from the oil andwater repellent. Textile and garment manufacturers would like theirpermanent press treated fabric to be oil and water repellent duringgarment manufacture. The polymers of this invention allow fabricstreated with such polymers to be cured at a low temperature withoutcuring any crease-resistant resin present.

A third deficiency of fabrics treated with present oilandwater-repellent polymers is that of oily-soiling retention. Oilrepellent fabrics, of course, tend to repel oily stains but it isimpossible to make them completely resistant to oily stains under allconceivable conditions. For example, oily stain will be forced into afabric if sufiicient pressure is applied even though the fabric willrepel the oily stain when no pressure is applied. During cutting andsewing operations, for example, fabrics can come into contact with oilymaterials under pressure. Such soiled fabrics containing an oil andwater repellent are more difficult to clean because the fabric tends torepel the cleaning medium also (detergent containing water). Suchfabrics are said to lack oily soil Washability. The polymers of thisinvention have better oily soil washability than presently usedpolymers.

A fourth deficiency of present oil and water repellents is that theyhave poor ability to resist abrasion. Most fabrics undergo a good dealof abrasive action during their lifetime. Rubbing during flexure orlaundering, Sliding of two fabrics together, for example on upholstery,and a variety of other mechanisms all tend to abrade the surfaces offibers in a fabric. Most, if not all, of the presently known fluorinatedoil and water repellents are not particularly resistant to abrasion.Most fabrics, therefore, sooner or later lose their coating of oil andwater repellent, especially at points of greatest wear and hence losetheir repellency to soiling by oilor water-based materials at these samepoints. The polymers of this invention resist such abrasive action morethan present oiland water-repellent polymers.

Additional deficiencies of present oil and water repellents include lackof durability of the repellent upon laundering or dry cleaning and lackof repellency toward dry-soiling, i.e., toward particulate matter. Thepolymers of this invention possess good durability and repellency towarddry-soiling.

3 SUMMARY OF THE INVENTION An oiland water-repellent polymer consistingessentially of:

(a) from 75% to 98% by weight of units derived from monomers ofstructure R,CH CH O CCH=CH wherein R is a perfluoroalkyl group of fromfour to fourteen carbons;

(b) from 25% to 2% by weight of units derived from monomers selectedfrom the class consisting of (1) ROCH=CH wherein R is selected from X(CF),,CH X being F or H and n one or two, and (CF CH-, and

(2) ROCF=CF wherein R is selected from R, as defined above, and F(CF mbeing from one to three; and

(c) from to by weight of units derived from monomers selected from theclass consisting of (1) CH CR CONHR OH,

(2) CHFOR CO R OH, and

(3) CHFCR CO R wherein R is H or CH R is an alkylene group of from oneto about four carbons, R is an alkylene group of from two to about fourcarbons and R is epoxyalkyl of at least three carbons; or

(4) mixtures of the above;

and wherein the total percent by weight of units present in thecopolymer is 100% Preferably the polymers have an inherent viscosity as0.5% solutions in trichlorotrifluoroethane at 30 C. not in excess of0.8, and most preferably in the range of 0.1 to 0.35.

DESCRIPTION OF THE INVENTION The polymers of this invention contain twoessential ingredients. The first is a monomer of structure wherein Rf isa perfluoroalkyl group of from four to fourteen carbons. From 75 to 98%by weight of such monomer must be present in the polymer. The secondessential monomer is chosen from ROCH CH where 'R is X(CF CH X being Hor F and n being one or two or (CF CH, and ROCF CF R is R, that is X(CF),,CH or (CF CH or F(CF 111 being from one to three. From 2 to 25% byweight of this monomer is used.

In the monomers RfCHZCHZOZCCHiHz, the perfiuoroalkyl group R ispreferably a straight chain group F(CF where s is from 4 to 14, but mayalso be branched perfluoroalkyl such as (CF CF(CF where s' is from oneto 11. In the preferred form of this invention, R is a mixture ofper-fluoroalkyl groups F,(CF where s is predominantly 6, 8 and 10.

The monomers R CH CH O CCH=CH are prepared by esterifying the alcohols RCH CH OH by one of several means, for example, reaction with acrylylchloride in the presence of a tertiary amine, reaction with acrylic acidin the presence of either an acid catalyst such as sulfuric ortoluenesulfonic acids or a tetraalkyl titanate (Werber, U.S. Pat.3,056,818), or by transesterification of the alcohols R CH CH OH with analkyl acrylate such as the methyl or ethyl esters in the presence of anacid or a tetraalkyl titanate (Haslam, U.S. Pat. 2,822,- 348). Thealcohols R CH CH OH are known compounds, see for example Day, U.S. Pat.3,283,012.

The monomers R,CH CH O CCH=CH may also be prepared by reaction of theiodides R CH CH I with an alkali metal salt of acrylic acid, using theprocedure of Fasick, U.S. Pat. 3,239,557.

It is essential in this invention that the acrylic acid ester monomers R'CH CH O CCH=CH be used. The corresponding methacrylic acid esters 4 donot result in polymers giving the desired results. The acrylic acidesters must also have the two methylene groups between R; and the estercarbonyl group. For when either of the known groups of acrylic acidesters R,CH O CCH=CH (U.S. Pat. 2,642,416) or 7:3 or more (U.S. Pat.3,102,103) is substituted for the monomers R 'CH- CH O CCH CH thedesired results are again not obtained.

The other essential monomer in the present polymers is the 'vinyl ethers-ROCH=CH or ROCF=CF The monomers ROCH CH may be any one of X(CF CHOCH=CH X=F or H, n=1 or 2, or (CF CHOCH=CH This group of monomersincludes HCF CH OCH=CH HCF CF CH OCH=CH and ('CF 'CHOCH=CH Of thisgroup, the preferred monomers are CF 'CH OCH=CH and particularly theformer.

These vinyl ethers are prepared from the corresponding alcohols CF CHOH, CF CF CH OH,

m=13 This group of monomers includes Most of these monomers are alsoknown. Those containing the methylene group -CH adjacent to oxygen areprepared by reaction of the sodium salt of the alcohols X(CF CH OH or(CF CHOH with tetrafluoroethylene, as taught by Dixon in U.S. Pat.2,917,548. The monomers F(CF OCF=CF are prepared by a different route.The most convenient method is that taught by Harris and McCane in U.S.Pat. 3,132,123, namely reaction of an acid fluoride F(CF COF with cesiumfluoride and hexafiuoropropylene oxide to form hydrolysis to the acidF(CF OCF(CF )CO H followed by pyrolysis of the acid to the olefin F (CFOCF=CF Other references teaching reaction of acid fluorides F(CF COFwith hexafluoropropylene oxide are Moore et al., U.S. Pat. 3,250,808 andMoore, French Pat. 1,362,548. Other disclosures of conversion of theacids or acid fluorides to olefines are contained in Fritz et al., U.S.Pat. 3,114,778; Fritz et al., U.S. Pat. 3,291,843, Lorenz, U.S. Pat.3,321,- 532; Harris and McCane, U.S. Pat. 3,180,895.

It is essential in the present invention that at least 2% by weight ofthe monomers ROCH CH or R'OCF=CF and no more than 25% of such monomersbe present. If less than 2% or more than 25 of such monomers arepresent, the desirable properties of the polymers are no longerobtained. The preferred concentration of these monomers is in the rangeof 3 to 10%.

Although it has not been found to be essential, it is often desirable toinclude in the polymers of this invention small amounts of certainmonomers which can lead to greater durability to dry-cleaning andlaundering. These monomers are preferably N-hydroxyalkyl acrylamides ofstructure CHFCR CONHR OH, hydroxyalkyl acrylic esters of structure CH CRCO R OH or epoxyalkyl acrylic esters of structure CH CR CO R where, inall cases, R is H or CH R in the amides is hydroxyalkyl of one to aboutfour carbons, R in the esters is hydroxyalkyl of two to about fourcarbons and R is an epoxyalkyl group of three or four carbons. Some ofthese monomers are commercially available, e.g. N-methylol acrylamide,N-methylol methacrylamide, 2-hydroxyethy1 acrylate, 2- hydroxyethylmethacrylate, glycidyl acrylate and glycidyl methacrylate. The otherhydroxyalkylamides are readily available by reaction of acryloyl ormethacryloyl chloride with hydroxyalkylamines such as ethanolamine,2-hydroxypropylamine, 3-hydroxypropylamine, Z-hydroxybutylamine,3-hydroxybutylamine or 4-hydroxybutylamine. Other hydroxyalkyl acrylatesor methacrylates are available by esterification of one mole of acrylicor methacrylic acid with one mole of diols such as 1,2-propylene diol,1,3-propylene diol, 1,2-butylene diol, 1,3- butylenediol or 1,4-butylenediol. Other epoxyalkyl esters are available from the epoxy butanols.

Of these monomers, the commercially available monomers are preferred,i.e. N-methylol acrylamide or methacrylamide, 2-hydroxyethyl acrylate ormethacrylate or glycidyl acrylate or methacrylate.

Mixtures of two or more of these monomers may be used and, in somecases, such mixtures are preferred, for example equal weights ofN-methylol acrylamide and 2- hydroxyethyl methacrylate.

It is necessary to use 0.1% by weight of such monomers to obtain anynoticeable effect. There is no benefit in using more than 5% and largeramounts have undesirable effects on the polymer properties. About 0.5 ofsuch monomers is preferred.

As noted earlier, these monomers are optional in the polymers of thisinvention. Perfectly satisfactory durability exists to laundering whenthey are completely absent although a better, more durable product maybe available when they are present.

No significant amounts of monomers other than the aforementioned typesshould be present in the polymers of this invention, as indicatedearlier, or the desirable properties will belost.

Although the polymers of this invention may be prepared by solutionpolymerization techniques Well known in the art, it is preferred to useaqueous emulsion techniques. In the broadest sense, any known freeradical initiator may be used, including both water soluble and waterinsoluble types. Among the water soluble types are inorganic peroxidessuch as sodium peroxide, barium peroxide or ammonium or potassiumpersulfate and water soluble azo compounds such asazobis(isobutyramidine) dihydrochloride. Among the water insoluble typesare peroxy anhydrides such as benzoyl peroxide, peroxy esters such astert-butyl peroxy pivalate, tert-butyl peroxy benzoate, hydroperoxidessuch as tert-butyl hydroperoxide, ditertiary alkyl peroxides such asditert-butyl peroxide, or water insoluble azo compounds such as azobis(isobutyronitrile), azobis(dimethylvaleronitrile) and the like. Redoxinitiators such as the combination of ammonium persulfate, sodiumbisulfite and ferrous sulfate are also useful.

In general, the Water soluble initiatorazobis(isobutyramidine)dihydrochloride is the initiator of choice.

The polymerization temperature is, quite naturally, chosen to suit theinitiator being used. Those skilled in 6 the art are well aware of thetemperatures appropriate to each of the aforementioned initiator types.

The polymerization is carried out by first emulsifying the monomers inwater, then bringing the reaction mass to the desired temperature andadding the initiator. It may be desirable, albeit not essential, tohomogenize the monomer-water mixture before heating. As many of themonomers ROCH CH and ROCF=CF as earlier defined are relatively lowboiling compounds, often lower boiling than the desired polymerizationtemperature, provision should be made to retain these monomers in thereaction system. This is readily accomplished by use of either anefiicient reflux condenser on the reaction vessel or by using a sealedautoclave for the polymerization.

Emulsifying agents must, of course, be used to obtain aqueous emulsions.Either cationic or anionic types are more preferred than the nonionictypes. Mixtures of nonionics with either other type may be used. Usefulcationic types are the well-known quaternary ammonium salts of longchain fatty amines,

where R is an alkyl group of at least twelve carbons. In general, R is alower alkyl group such as methyl and X- is an inert anion such aschloride ion. A typical group of such agents are the ammonium salts soldby the Armour Co. under the trade name Arquad. These are n-alkyltrimethyl ammonium chlorides where the alkyl has from 12 to 18,preferably 16, carbons. These are the preferred cationic dispersingagents. Another type of cationic agents is the acetate salts of n-alkyldimethylamines Where alkyl again contains 12 to 18 carbons. These saltsare perfectly suitable insofar as the polymerizations are concerned buthave a slight deleterious effect on oily-soil washability of the productpolymers on fabric, hence are not preferred.

Useful anionic emulsifying agents include both the alkali metal salts ofalkanesulfonic acids and alkali metal salts of monoalkylsulfuric acidesters, where alkyl again is from 12 to 18 carbons. Fatty acid soaps maybe used, provided the fatty acid is relatively free of unsaturatedacids.

It is generally preferable, if the most advantageous polymer propertiesare to be obtained, that the inherent viscosities of the polymers ofthis invention be below 0.8, when measured at 30 C. as 0.5% solutions intrichlorotrifluoroethane. Inherent viscosity is determined by theformula 1 V VZ '6 ln where Vi is the inherent viscosity, C is thepolymer concentration in grams per ml. of solution, V is the viscosityof the solution, V0 is the viscosity of the solvent and In is thenatural logarithm.

In general, very little has to be done to keep inherent viscosity below0.8 due to the nature of the reacting monomers, vinylethers being rathermore eflicient chain transfer monomers than acrylic esters. Ifnecessary, small amounts of chain transfer agents such as dodecylmercaptan may be added to control molecular weight, hence inherentviscosity.

For use in oil and water repellent formulation, the polymer emulsionsobtained by the above procedures are usually used directly in the padbath without isolation of the polymer.

The compositions are applied preferably as an aqueous dispersion bybrushing, dipping, spraying, padding, rollcoating or by any combinationof these methods. For example, the prepared concentrated dispersion ofpolymer composition may be used as a pad bath by diluting it with waterto a solids content of 0.1% to 10% by weight of the bath. The textilematerial is padded in this bath, and is then freed of excess liquid,usually by squeeze rolls, so that the dry pickup (weight of dry polymeron fiber) is between 0.1% and 10% by weight of the fiber. The treatedmaterial is then dried by heating, say in an 7 oven at 135 to 172 C.until dry. The dry fabric is oil and water repellent without furtherheating but such further heating may increase the degree of repellencysomewhat. The textile material will retain repellency even after manylaunderings or dry-cleanings.

It is common practice to treat fabrics with several agents at the sametime. These agents may include softeners, crease resistance agents,wetting agents, antistatic agents, resin finishes, soil release agents,flame retardants and the like. When used in the presence of such agents,lower concentrations of the polymers of this invention may be requiredto obtain equivalent repellency than when used alone. It is also commonpractice to add auxiliary water repellents to treating baths. Ingeneral, far more of the polymers of this invention are required toobtain maximum water repellency than maximum oil repellency.Commercially, it is cheaper to add only as much polymer as is requiredto obtain the desired oil repellency, than to add the far cheaper waterrepellents to bring up water repellency to the desired level.

More recently, another development has occurred in the textile trade,the permanent press treatment, as taught, for example, in US. Pat.2,974,432. In this treatment, a permanent press resin such as describedin US. Pat. 3,049,446 is coapplied along with the polymers of thisinvention. In some cases such resins are not cured, however, until thetextile is fabricated into the finished article. It is important,therefore, that the textile is repellent, without anything more thandrying, which occurs when using the polymers of this invention, as aboveindicated.

Suitable substrates for application of the polymers of this inventionare fibers, yarns, fabrics and articles made of filaments, fibers oryarns derived from natural, modified natural or synthetic polymericmaterials or from blends of these. Examples are cotton, silk,regenerated cellulose, nylon and like synthetic polyamides,fiber-forming linear polyesters, fiber-forming polyacrylonitrile andmodified acrylonitrile polymers, cellulose nitrate, cellulose acetate,fiberglass, paper, leather and the like. These may be in many forms ofknit and woven fabrics, including sateen, poplin, broadcloth, jean clothgabardine, upholstery materials, as well as non-woven fabrics and thelike used to fabricate rainwear, work clothing, suiting, femaleclothing, tenting, autobody tops, furniture upholstery, draperies and avariety of others.

The polymers of this invention overcome essentially all of theobjections to earlier fluorinated oil and water repellents.

EXAMPLE I Preparation of copolym-ers of this invention (a) A dispersionof 144 parts F CH CH O CCH CH 16 parts of a 50% aqueous solution ofoctadecyltrimethyl ammonium chloride and 80 parts water was prepared,then diluted with 48 parts further water. The dispersion was purged withnitrogen for 30 min., then 0.095 part 2-hydroxyethyl methacrylate and0.145 part 60% aqueous N-methylolacrylamide were added and purged for anadditional 30 min. Then 16 parts trifluoroethyl vinyl ether were addedand the resulting mixture was added to 300 parts further water. Whilemaintaining the mass under a slight positive nitrogen pressure and underan efiicient reflux condenser, the temperature of the mass was raised to65 C. and 0.32 part azobis (isobutyramidine)dihydrochloride was added.Further like additions of azo compound were made after 20 and 60minutes, after which the mass was maintained at 65-70" C. for eighthours.

The resulting polymer latex contained 25.52 parts polymer per 100 partslatex, corresponding to a 96.4% monomer conversion. A sample of driedpolymer had an inherent viscosity of 0.70 as a 0.5% solution intrichlorotrifluoroethane at 30 C. Nuclear magnetic resonancespectrographic analysis of a hexafluorobenzene solution of the polymerindicated it contained 2.75% by Weight trifiuoroethyl vinyl ether.

The composition of the polymer comprised units of the monomers shown asfollows in the weight percents shown:

Percent 'CF CH OCH CH 2.75 CH CHCONHCH OH 0.25 CH =C (CH CO CH CH OH0.25

(b) The polymerization procedure of part (a) was repeated except thatthe fluorinated acrylate of part (a) was replaced with F(CF CH CH OCCH=CH and the 2-hydroxyethyl methacrylate and aqueousN-methylolacrylamide were omitted. The resulting polymer contained about96% by weight of units derived from the fluorinated acrylate and about4% by weight of units derived from the CF CH OCH CH The inherentviscosity was 0.68.

(c) The polymerization procedure of part (a) was repeated except thatthe fluorinated acrylate of part (a) was replaced with F (CF CH Cl-l OCCH=CH (wherein n represents the numerals 6, 8, 10, 12 and 14 in theapproximate weight ratio 35/30/18/8/3). The resulting polymer containedabout 6% by weight of units derived from the fluorinated acrylate, about4-5% by weight of units derived from the tained about 97.5% by weight ofunits derived from the fluorinated acrylate, about 2% by weight of unitsderived from the CF CH OCH=CH and about 0.25% each of the hydroxyethylmethacrylate and methylolacrylamide.

(e) The polymerization procedure of part (a) was repeated except thatthe fluorinated acrylate of part (a) was replaced with F(CF CH CH O CHCI-I '[wherein n is defined as in part (c)] in an amount of about 131.2parts; and the amount of the trifluoroethyl vinyl ether employed was28.8 parts. The resulting polymer contained about 92% by weight of unitsderived from the fluorinated acrylate, about 8% by weight of unitsderived from CF CH OCH=CH and about 0.25% each of the hydroxyethylmethacrylate and methylolacrylamide.

(f) The polymerization procedure of part (a) was repeated except thatthe fluorinated acrylate of part (a) was replaced with F(CF ,CH CH OCCH=CH [wherein n is defined as in part (c)]; and the 2-hydroxyethylmethacrylate and aqueous N-methylolacrylamide Were omitted. Theresulting polymer contained about 96% by weight of units derived fromthe fluorinated acrylate and about 4% by weight of units derived from CFCH OCH=CH The polymer had an inherent viscosity of 0.22.

EXAMPLE II Employing the parts and procedure of Example 1(a), except asindicated, the following polymers were prepared. These polymers are notones which fall within the scope of this invention and were prepared inorder to carry out the comparison tests found in the subsequentexamples:

(a) A copolymer of about 94-5% by weight of units 9 derived from F(CF CHO CCH=CH about 6% by weight of units of CF CI-I O--CH=CH and about 0.25%each by weight of units derived from Z-hydroxyethyl methacrylate andN-methylolacrylamide, having an inherent viscosity of 0.80 was preparedby polymerizing the above monomers as described in Example 1(a).

(b) 156.8 parts of F(CF CH 'CH O CCH=CH [wherein n is defined as in part(c) of Example I], 3.2 parts of CF CH OCH=CH and the same amounts of2-hydroxyethyl methacrylate and N-methylolacrylamide as shown in ExampleI(a) were polymerized as described in Example 1(a). The resultingpolymer contained only about 1% by weight of units derived from (c) Acopolymer of F(CF ),,CH 'CH O CCH=CH [wherein n is defined as in ExampleI(c)] in about 99.5% by Weight units and about 0.25 by weight each ofunits derived from 2-hydroxyethyl methacrylate and N-methylolacrylamidewas prepared by reacting the monomers as described in Example I( a).However, the trifiuoroethyl vinyl ether was omitted. The resultingcopolymer had an inherent viscosity of 0.47.

EXAMPLE III The water repellency of the polymer of Example I(c) wascompared with that of the polymer of Example II(c) by preparing padbaths with formulations containing each. Each formulation was paddedonto a 65/35 polyethylene terephthalate/cotton-Thermosol-dyed poplinfabric until a desired percent wet pick-up on weight of fabric (OWF) ofthe polymer and other dispersants of the formulation was obtained on thefabric. The desired amount of pick-up is obtained by adjustment of thesqueeze rolls. The treated fabrics were then air-dried and cured atabout 350 F. for minutes. They were then tested for their initial oiland water repellency and were retested after subjecting them to varioushome washtumble dry or air-dry or dry-cleaning procedures as describedbelow.

The formulations employed and the percent on weight fabric pick-up areshown in the following table. Four formulations were used labeled A, B,C, and D, i.e., Formulations A and B contained the polymer of ExampleI(c) and were identical except that the amount of the polymer inFormulation A was sufficient to produce a 2% OWF pick-up on the fabric,while the amount of the polymer in Formulation B was sutficient toproduce a 3% OWF pick-up on the fabric. Formulations C and D containedthe polymer of Example II(c) and were identical except for the amountsof polymer in each.

Amount of formulation component on fabric (percent OWF) Component offormulation A B C D A 6.54% active ingredient dispersion of the polymerof Example 2 3 C m nN Table I below shows the oil and water repellenciesof the fabrics treated with Formulations A, B, C and D initially, afterone home wash-air dry, after one home washtuble dry, after five homewash-tumble dry cycles, after one dry cleaning, and after five drycleanings.

The oil repellencies were determined using Test Method No. 118-1966T ofthe American Association of Textile Chemists and Colorists, modified inthat the oils used contained dissolved therein a blue oil-soluble dyeand the determinations were made after three minutes, rather than the 30sec. required by the aforementioned test. Oilrepellency figures run from1-6; 6 being good repellency, 1 being poor. Water repellencies weredetermined by Test Method No. 221952 of the aforementioned association.Water-repellency figures run from 0 to 100 being good repellency, 0being poor.

Home laundering tests were carried out in a Kenmore washer Model 600loaded with a 4-lb. load, with 29 g. of Tide. The wash is set at hot (12min. cycle) and a warm rinse (12 min.). The total washing and rinsingtime is 40 minutes. In the home laundering air-dry test, the spundryfabrics are dried at ambient temperatures. In the home launderingtumble-dry test, the spun-dry fabrics are dried at 156-l60 F. in a homedrier with tumbling.

The dry-cleaning test consists of agitating the sample for 120 minutesin tetrachloroethylene containing 1.5% (weight/volume) of a commercialdry-cleaning detergent (R. R. Street Co., 886 Detergent), extractionwith tetrachloroethylene, drying for three minutes at 66 C. in a drumand followed by a 15-second pressing at 149 C. on each side of thefabric.

The oil and water repellencies of the fabrics before and after theabove-described tests are shown in the following Table I:

1 Example To polymer, 2% OWF. 2 Example To polymer, 3% OWF. 3 ExampleIIc polymer, 2% OWF. 4 Example He polymer, 3% OWF. 6 Home wash air dry.

6 Home wash tumble dry.

7 Dry-cleaning.

These formulations contained no added water repellent, as is usually thecase in most oil/water-repellent formulations for commercial textiletreatment. Hence water repellency is not as good as would be expected ina full commercial formulation.

EXAMPLE IV Aqueous emulsions of the polymers obtained in Examples I(c),I(d), I(e) and II(b) were prepared in which the emulsion contained 5.4%by Weight of F(CF CH CH O CCH=CH in polymerized form.

Formulations containing the emulsions (or dispersions) meme obtained inthe preceding paragraph were prepared as E Q described in Example IIIusing the same ingredients N (other than the polymers). However, theformulations g i were made up such that the percent pick-up on weight ofg 511 Q fabric of the polymers was 1, 2 and 4%, while the per- '56 Z acent pick-up OWF for the other components of the formua. E, g E lationwas in each, 12% OWF for the crease-proof resin, F i:

2.4% OWF for the catalyst, and 0.05% OWF for the 513 g Q stabilizer. g;g a

The formulations prepared above were tested for their 20 5 oilrepellency before and after laundering and cleaning a. tests carried outacocrding to the description in Example E, z wh III. The results of suchtests are shown in Table II. E

EXAMPLE v Q3 An emulsion (labeled the First Emulsion in Table III O whimbelow) was prepared containing 6.48% active ingredient e of the polymerof Example I(c) and containing 7.8% acg l tive ingredient of a copolymerof 2-ethylhexyl methacrylj: ate and N-methylolacrylamide (in which theamount of 33 Q N-methylolacrylamide in the copolymer was about 0.5% figg by weight). 55 E m A similar emulsion (labeled the Second Emulsion ing; g H Table III below) was prepared which contained only g; g Q 6.48%active ingredient of the. polymer of Example I(c). 55 0 2 Threedifferent formulations were prepared from each a? E of the two emulsions(resulting in 6 formulations in all). 5.5.

One of each set of three was prepared to result in a E g5; percentpick-up on Weight of fabric of the polymer or E polymers in theformulation of 2%. Another of each set Q {5 2 of three was prepared toresult in a percent pick-up on H 3 weight of fabric of the polymer orpolymers in the formu- 0 lation of 3%. The last of each set of three wasprepared a to result in a percent pick-up on weight of fabric of E thepolymer or polymers in the formulation of 4%. Each g g of the sixformulations contained a water repellent (a i E 3 Q NHHO 25% solidsdispersion in water in which the solids were E e 3 47.5% tris(methoxymethyl) tris(behenoyloxymethyl) f .E a g E melamine, 47.5% parafiin wax,and 5% dimethyl fatty 40 a HF amine acetates) in an amount sufficient toresult in an fio g E; No on-weight fabric pickup of about 2%; awash/Wear resin E of triazine-formaldehyde condensate (Aerotex 23 Spe- Eg .4

cial) in an amount sufficient to result in an on-Weight 2 71 NNMH fabricpick-up of about 5%; and the catalyst and stabilizer E 2 g used in theformulations described in Example III in amounts sufi'icient to resultin an on-weight fabric pick- #1 5g up of about 1% and 0.04%,respectively.

Each of the six formulations was applied to the fabric 5 E i i used inExample III and the fabrics then dried at 340 E E E F., then cured fortwo minutes at the same temperature. l i E The fabrics were tested forthe initial oil and water 5 l i i repellency, for their repellency after1 dry-cleaning, and u for their repellency after 1 standard laundering(which consisted of agitating the treated fabric for 40 min. at Qfifl C.to 100 C. in Water containing 0.1% by weight 588g neutral chipsoap+0.05% soda ash, rinsing with 60 C. 55m water three times, spindrying, then pressing on each face at 300 Eizo" F. for 30 sec.) some Theresults are shown in Table III. 60 o fg Three formulations wereprepared. Each contained a sufficient sodium acetate to provide a 4%pick-up on G5 L 0 weight of fabric of the acetate, suflicient aceticacid to E 5 provide a 0.3% pick-up on weight of fabric of the acid, 3and sufficient long chain alkyl pyridinium chloride water E 51 225repellent to provide a 4% pick-up on weight of fabric :5 of thechloride. In addition, one formulation contained S sufficient 6.5%active ingredient emulsion of the polymer 8 of Example I(c) to provide a2% pick-up on weight of QEEIE fabric of the polymer. The secondformulation contained i a sufficient amount of said polymeric emulsionto provide 5 iii; a 4% pick-up. The last formulation contained asufiicient 3 3 5 TABLE III Water repellency Oil repellency WaterIBDQHGIICY Initial Oil repellency after Initial after water Formulationcontainingrepellency 3 SW 1 DC repellency 3 SW 1 DC First emulsion in 2%OWF formulation 4 4 6 80 80 80 First emulsion in 3% OWF formulation. 6 690 80 80 First emulsion in 4% OWF iormulatiom 5 6 6 80 80 80 Secondemulsion in 2% OWF formulation. 3 3 3 80 80 80 Second emulsionin 3% OWFformulation 4 4 5 80 80 80 Second emulsion in 4% OWF formulation 5 5 590 80 80 amount of said polymeric emulsion to provide a 5% TABLE Vpick-up. No. cycles abrasion: Oil repellency Each formulation wasapplied to 9 oz. sateen, dried 0 and cured as described in Example V.The treated fabrics 500 were tested for their initial oil and waterrepellency, 1000 their repellency after 15 launderings, and theirdynamic 1500 absorption. The results are shown in Table IV following:5000 EXAMPLE IX Pad baths were prepared with the formulations shown 1Federal Specifications, Textile Test Methods COCT191BMethod 5500.1.6American Association of Textile Chemists & Colorists, Method 70B-19 7.

EXAMPLE VII A pad bath was prepared and applied to 8.4 oz./yd. of 100%nylon 66 tricot (commonly used on automobile upholstery) giving 0.22%loading of the fluoropolymer of Example I(c) on weight of fabric. Afterdrying and curing as described in Example V, the fabric had anoilrepellency of 6 and a water repellency of 90. After 5,000 cycles in aWyco abrader, the oil and water repellency were 5 and 50, respectively.

I EXAMPLE VIII ,An emulsion was prepared of the polymer of Example I(c)as described for the preparation of the formulation labeled A in ExampleIII. A cotton/polyester (35/65) poplin fabric was treated with theemulsion, cured for 10 min. at 340 F., given one dry-cleaning, thenabraded in a Wyco abrader. Samples were evaluated for oil repellency atvarious points. The results are shown inTable V.

below. Textiles were padded with these baths and the wet pick-up wascontrolled to give the concentrations on fabric shown by adjustment ofthe squeeze rolls. The treated fabrics were then placed in an ovenheated at 275 F. for specific times and the indicated repellencies weredetermined. Fabrics in the oven 40 sec. or less were still wet. In allcases, the fabrics were air dried in a constant humidity room untilconstant weight is reached before the repellency was determined. Theresults are shown in Table VI.

FORMULATIONS Percent OWF Component A B C D E Fluoropolymer dispersion A1 2 Fluoropolymer dispersion B 2 2. 6 3. 6 Fluoropolymer dispersion 0 2.5 3 5 Permairesh 183 12 12 Catalyst 4 2.3 2.3 2.3 2.3 2.3 Stabilizers0.04 0.04 0.04 0.04 .04

1 Fluoropolymer dispersion A 6.54% A. I. dispersion of the polymer ofexample 10 2 Fluoropolymer dispersion B6.21% A. I. dispersion of thepolymer of example 1C.

5 Fluoropolymer dispersion C6.21% A. I. dispersion of the polymer ofexample 20. I

4 Pennafresh 183, catalyst and stabilizer as identified in example III 1The fabrics treated were:

Fabric A65/ 35 polyethylene terephthalate/cotton- Thermosol dyed poplin.

Fabric B-undyed, mercerized cotton, neutral pH, no whiteners, 1.6yards/1b., 46 inches wide.

The results are shown below. In these tests, two oil repellency testswere used; 30 sec. refers to Test Method No. 118-1966T as written; 3mini refers to the 3 minute 15 variation using blue dyed oils describedin Example III. Water Repellency was determined as in 'Example III.

Formulation Water repellency On Fabric A, oil repellency develops to amuch higher degree before the fabric is actually dry (time 40 sec. orless) with Formulations B and C of this invention than with FormulationsD and E which are outside this invention. Likewise, on Fabric B, thewater repellency develops more quickly and to a higher degree withFormulation C than Formulation E.

EXAMPLE X A set of cotton/polyester (35/65) poplin fabrics were treatedwith the formulation described as Formulation B in Example III (whichcontains the polymer of Example 1(0)), and a second set of the samefabric was treated with a formulation identical to that of Formulation Bexcept that the polymer in Formulation B was replaced with the polymerof Example II(c) (a homopolymer of F(CF ),,CH CH O CCH=CH This secondformulation is identified as Formulation B in Table VII below.

Samples of each set of treated fabrics were then subjected to repeatedhome laundering with tumble dry as described in Example III with the oilrepellencies being determined periodically. A second set of samples ofeach set of fabrics was subjected to the dry-cleaning treatmentdescribed in Example HI with oil repellencies again being determinedperiodically. The results are shown in Table VII.

Home wash-tumble dry. 2 Dry-cleanings.

Notethat Formulation B, where the fiuorinated-polymer contains thedurabilizers hydroxyethyl methacrylate and methylolacrylamide is aboutone oil unit more durable to laundering than Formulation B where thedurabilizers are absent. Even when the durabilizers are ab-' sent,reasonable results are obtained. On the other hand, these two addedmonomers have no beneficial effect on durability to dry-cleaning.

Note that Formulation B is about one oil unit more durable to launderingthan Formulation B.

EXAMPLE XI A cotton/ polyester (35/65) poplin fabric was treated withFormulation A of Example III and cured as described therein. The fabricwas then subjected to the drycleaning procedure of Example III, omittingthe pressing step. Instead, after removal of the excess solvent, the

fabric was placed in a flat bed press for a specified number of secondson each side of fabric and then the oil repellency was determined. Theresults are shown in 1 Before dry-cleaning.

Note that oil repellency recovers with essentially no pressing afterdry-cleaning.

EXAMPLE XlI Oily soil washability Circular swatches of fabric identicalto the fabric used in Example III were treated with the formulationsdescribed as follows. Each formulation was identical to that describedfor the formulations shown in Example 111 except the polymers used inthe formulations of Example III Were replaced by the polymers set forthfollowing in the amounts suflicient to provide the on-weight-of-fabricpick-up of polymer set forth following:

The polymer of Example I(a) was used in one formulation in an amountsuflicient to provide an OWF pick-up of 1%. The same polymer was used inthree other formulations in amounts sufiicient to provide OWF pick-upsof 2, 3 and 4%, respectively. The polymer of Example I( b) was used infour other formulations in amounts sufficient to provide OWF pick-ups ofpolymer of 1, 2, 3

and 4%. The polymer of Example II(a) was used in four other formulationsin amounts sufiicient to provide OWF pick-ups of polymer of 1, 2, 3 and4 Each treated fabric was soiled by vacuum sucking dyed (blue,oil-soluble dye) Nujol through the cloth. Each fabric was then washed byplacing it in an 8 oz. jar with ml. detergent solution (1.5 g./l.) andshaken in a horizontal position in a thermostat bath, at about 50- 55 C..The samples were then rinsed free of detergent and dried to constantweight. From the weightsof fabric Sample before soiling and aftersoiling, the percent oil pick-up and percent oil retention, on weight offabric, were calculated.

A second set of fabrics treated with the formulations described abovewas first subjected to one home laundering-tumble dry as described inExample III then subjected to the soiling procedure described above. Thepercent oil retention of each fabric is shown in Table IX following.

TABLE IX 18 hydroxyethyl methacrylate and (d) 0.725 part 60% aqueousN-methylolacrylamide. The resulting polymer Fabric containing polymer orFabric containing polymer of Fabrics Containing polymer of Example Ia,percent oil retention Example Ib, percent oil retention Example IIa,percent oil retention Formulation Measured with- Measured with- Measuredwithresulting in OWF out laundering Measured after out launderingMeasured after ou t launder ng Measured after pick-up of prior totesting laundering prior to testing laundering prior to testinglaundering These results show that the polymers of this invention (1(a)and I(b)) have inherently lower oil retention than does a polymer not ofthis invention (II(a)).

EXAMPLE XIII Example XII was repeated using two wash temperacient toproduce the pick-up on weight of fabric (OWF) shown in Table X below.The fabrics were evaluated only after one home laundering with tumbledry. The results are described in Table X following.

(D) (a) 144 parts F CF CH CH O CCH=CH (b) 16 parts CF CH OCH=CH (c)0.475 part Z-hydroxyethyl methacrylate, and (d) 0.725 part 60% N- TABLEX Fabric treated 1 with the formula- V Percent 011 tion containingPercent Wash retention the polymer of emulsion, temp., Detergent afterone example OWF C. cone., g./l. HWTD v 2 50 0. 42 30 3 50 0. 42 25 2 750. 42 23 Ib 3 75 0. 42 12 2 50 1. 5 11 3 50 1. 5 8 2 75 1. 5 7 3 75 1. 57

2 50 0. 42 39 3 50 0. 42 34 2 75 0. 42 37 Ha a 75 o. 42 3o 2 50 1. 5 273 50 l. 5 25 2 75 1. 5 26 3 75 1. 5 14 I It is readily apparent thatunder any set of conditions,

EXAMPLE XIV Using the polymerization procedure set forth in Example .I,polymers were prepared using the monomer concentrations set forth inparts A-J. (n in each part is defined as in Example 1(0)).

(A) (a) 132.8 .parts F(CF ),,CH CH O CCH=CH (b) 27.2 parts CF CH OCH=CH(c) 0.475 part 2- methylolacrylamide. The resulting polymer contained1.25% (d), by weight.

(E)(a) 144 parts F(CF ),,CH CH O CCH=CH (b) 16 parts CF OCF=CF (c) 0.095part 2-hydroxyethyl methacrylate, and (d) 0.145 part 60% aqueous N-methylolacrylamide. The resulting polymer contained 0.25% each of (c)and (d) by weight.

(F )(a) 130.9 parts F(CF CH CH O CCH=CH (b) 29.1 parts CF OCF CF (c)0.095 part 2-hydroxyethyl methacrylate, and (d) 0.145 part 60%N-methylolacrylamide. The resulting polymer contained 92.9% (a), 6.6%(b), 0.25% (c) and 0.25% (d), by weight.

(G) (a) parts F(CF ),,CH CH O CCH%I-I (b) 40 parts CF OCF=CF (c) 0.095part Z-hydroxyethyl methacrylate, and (d) 0.145 part 60%N-methylolacrylamide. The resulting polymer contained 0.25% (c) and (d)each, by weight.

(H) (a) 144 parts F(OF ),,CH CH O CCH=-CH (b) 16 parts CF (CF OCF=OF (c)0.095 part Z-hydroxyethyl methacrylate, and (d) 0.145 part 60%N-methylolacrylamide. The resulting polymer contained 0.25 (c) and ((1)each, by weight.

(I) (a) 130.9 parts F(CF CHgCH O CCH=CH (b) 29.1 parts CF (CF OCF=CF (c)0.095 part 2-hydroxyethyl methacrylate, and (d) 0.145 part 60% N-methylolacrylamide. The resulting polymer contained 0.25% (c) and (d)each, by weight.

(J (a) 120 parts F(CF ),,CH CH O CCH=CH (b) 40 parts CF (OF OOF=CF (c)0.095 part 2-hydroxyethyl methacrylate and (d) 0.145 part 60% N-methylolacrylamide. The resulting polymer contained 0.25% (c) and (d)each, by weight.

Each polymeric emulsion obtained in parts A] above was diluted to anemulsion containing 6.21% active ingredient of the polymer to obtainformulations resulting in percent pick-up of each polymer of 1, 2 and 4%on weight of fabric ('OWF). Each formulation also contained 12% OWF ofthe crease-proof resin that was used in the formulations of Example III,2.3% OWF of the catalyst that was used in the formulations of ExampleIH, 0.05% OWF of the stabilizer that was used in the formulations ofExample 111, and in addition, contained 0.4% OWF acetic acid.

Each formulation was applied to the fabric used-in Example III asdescribed therein and cured and tested for oil repellency as describedtherein. The results are shown below in Table XI.

A. Example Ia was repeated using (a) 144 parts F(OF ),,CH 'CH O CCH=CH(defined as in Example I(c)), (b) 16 parts CF CH OCF=CF (c) 0.095 part2-hydroxyethyl methacrylate, and (d) 0.145 part 60% Nrnethylolacrylamide The resulting polymer contained 0.25% (c) and 0.25%(d), by weight.

B. Example Ia was repeated using (a) 131.2 parts F(CF ),,CH CH O CCH=CH(defined as in Example I(c)), (b) 28.8 parts CF CH OCF=OF (c) 0.095 partZ-hydroxyethyl methacrylate, and (d) 0.145 part 60% N-methylolacrylamide. The resulting polymer contained 0.25% (c) and 0.25%(d), by weight.

The emulsions obtained in these two polymerizations were diluted to 5.4%A1. of

incorporated into the formulation of Example XIV and applied as inExample XIV with the results shown in Table XII.

TABLE XII Repellencies Cone, Polymer percent Initial 1 HWAD 1 HWTD 1 DCexample OWF oil oil oil 011 l 2 l 1 XV A 2 2 4 4 4 6 3 5 5 1 3 0 2 p 2XVB 2 5 2 4 5 4 6 3 5 5 EXAMPLE XVI Using the procedure of Example XII,oil retention was determined for a number of polymers of the previousexamples. All of these polymers were applied as described in ExampleXII. The results are shown in Table XIII.

TABLE XIII Percent Percent oil Polymer example OWF retention EXAMPLEXVII Bleached, unsized paper was immersed in an aqueous dispersioncontaining 0.25 by weight of the polymer of 2 .20 2. Example I(c) for 15'sec., passed through a'nip roll (120% wet pickup) and dried for threeminutes at C. The resulting paper contained 0.3% by weight p y Theresulting paper Withheld the No. 5 oil (dodecane) from oil repellencytest No. 118-1966T mentioned in Example III from penetration of thepaper for three minutes. A lactic acidlink mixture failed to penetratefor about one minute.

Similarly, unbleached waterleaf kraft paper was treated to obtain 0.4%fiuoropolymer on weight of paper. The No. 8 oil (heptane) failed topenetrate after three minutes and the lactic acid/ink mixture requiredfive minutes for penetration.

The preceding.representativeexamples may be varied within thescope ofthe present total specification disclosure, as understood andpracticedby one skilled in the art, to achieve essentially the same results.

The foregoing detailed description has been given for clear ness ofunderstanding only .andno unnecessary limitationsare to be, -understoodtherefrom. The invention. is

not limited to the exactdetails shown and described, for obviousmodifications willoccur to those skilled in the art.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. An oiland water-repellent copolymer consisting essentially of (a)from about 75 percent to about 98 percent by weight of units derivedfrom monomers of the structural formula wherein R is a perfluoroalkylgroup of from four to fourteen carbon atoms; I M 1 (b) from about 25percent to about 2 percent by weight of units derived from monomersselected from the class consisting of 1) ROCH=CH wherein R is X(CF CH or(CF CH where X is F or H and n is one or two, or p (2) R0CF=CF whereinR" is F(CF or R where m is from one to three; and (c) from 0 percent toabout 5 percent by weight of units derived from monomers selected fromthe class consisting of 1 (1) CH =CR CONHR OH, (2) CH =CR CO R QH, (3.)CH CR CO R or (4) mixtures of the above wherein R is H or CH R isalkylene of one to four carbon atoms, R is alkylene of two to fourcarbon atoms, and R is epoxyalkyl of three to four carbon atoms;

.present ina weights ratio of 35/30/18/8/3.

4. The copolymer of claim 3, said copolymer having'an inherentviscosity: as 0.5% solutions'in trichlorotrifluoroethane at 30 C. ofless than 0.8. 2 I

5. The copolymer of claim 4 wherein the units defined in part (b) arederived from'ROCH=CH 6. The copolymer of claim 5 wherein the R group ofROCH=CH is CF CH I 7. The copolymer of claim 1 wherein the units definedin part (b) are derived frorri'ROCH=CH 8. The copolymer of claim 7, saidcopolymer having an inherent viscosity as 0.5% solutionsintrichlorotrifluoroethane at 30 C.'of less than 0.8. 2

9. The copolymer of claim 8 wherein the R group in ROCH=CH is CF CH 2110. An oiland water-repellent copolymer consisting essentially of (a)from about 75 percent to about 98 percent by weight of units derivedfrom monomers of the structural formula wherein R: is a perfiuoroalkylgroup of from four to fourteen carbon atoms;

(b) from about 25 percent to about 2 percent by weight of units derivedfrom monomers selected from the class consisting of 1) ROCH=CH wherein Ris X(CF CH or (CF CH- where X is F or H and n is one or two, or

(2) ROCF CF wherein R is 1 (CF or R where m is from one to three; and

wherein the total percent by weight of units present in the copolymer is100 percent.

11. The copolymer of claim 10 wherein R in the units defined in part (a)of claim 10 has the formula F(CF wherein s is a cardinal number of fourto fourteen.

12. The copolymer of claim 11 wherein s in the formula F(CF has thenumerical values 6, 8, 10, 12 and 14 present in a weight ratio of 35/30/ 18/ 8/ 3.

13. The copolymer of claim 12, said copolymer having an inherentviscosity as 0.5% solutions in trichlorotrifiuoroethane at 30 C. of lessthan 0.8.

14. The copolymer of claim 13 wherein the units defined in part (b) arederived from ROCH=CH 15. The copolymer of claim 14 wherein the R groupof is CF3CH2.

16. The copolymer of claim 10 wherein the units defined in part (b) arederived from ROCH=CH 17. The copolymer of claim 16, said copolymerhaving an inherent viscosity as 0.5% solutions intrichlorotrifluoroethane at 30 C. of less than 0.8.

18. The copolymer of claim 17 wherein the R group of ROCH=CH is CF CH19. A textile fabric treated with the copolymer of claim 1.

20. A textile fabric treated with the copolymer of claim 10.

21. Paper treated with the copolymer of claim 1.

22. Paper treated with the copolymer of claim 10.

References Cited UNITED STATES PATENTS 2,991,277 7/1961 Schildknecht260-861 3,102,103 8/1963 Ahlbrecht et al 260-861 3,282,905 11/1966Fasick et a1 26086.1 3,347,812 10/1967 De Marco et al. 260-861 3,378,6094/1968 Fasick et al 26086.1 3,384,627 5/1968 Anello et al 260-86.13,459,696 8/1969 Read 260-861 HARRY WONG, JR., Primary Examiner U.S. Cl.X.R.

PEI-1050 UNITED STATES PATENT OFFICE 69 CERTIFICATE OF CORRECTION PatentNo. LEQJBZ Dated December 8. 1970 Inventor-(s) Ibgmag K, may Jr.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

In claim p (1), a single bond should follow the formula X(CF CH andshould appear x(g 2)nc 2 In claim 1, part (4), "wherein R should pertainto all of the claim, -not onl; "mixtures of the above".

In claim 10, part (1), a. single bond should follow the forum X(CF CHand should appear as I(CF CH Signed and sealed this 23rd day of March 1971 (SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SGHUYLERJR. Attesting OfficerCommissioner of Patents

